U.S. patent number 4,581,461 [Application Number 06/483,037] was granted by the patent office on 1986-04-08 for maleated siloxane derivatives.
This patent grant is currently assigned to National Starch and Chemical Corporation. Invention is credited to Dilip K. Ray-Chaudhuri, Robert D. Rossi.
United States Patent |
4,581,461 |
Rossi , et al. |
April 8, 1986 |
Maleated siloxane derivatives
Abstract
Maleated aminophenoxysiloxanes are prepared by reacting
diaminodiphenoxysiloxanes with maleic anhydride. In addition, the
resultant maleamic acid derivatives may be cyclized yielding
isomaleimide or maleimide siloxane derivatives.
Inventors: |
Rossi; Robert D. (Levittown,
PA), Ray-Chaudhuri; Dilip K. (Bridgewater, NJ) |
Assignee: |
National Starch and Chemical
Corporation (Bridgewater, NJ)
|
Family
ID: |
23918392 |
Appl.
No.: |
06/483,037 |
Filed: |
April 7, 1983 |
Current U.S.
Class: |
548/406; 556/419;
549/214 |
Current CPC
Class: |
C07F
7/0838 (20130101); C07F 7/0889 (20130101) |
Current International
Class: |
C07F
7/08 (20060101); C07F 7/00 (20060101); C07F
007/02 (); C07F 007/10 () |
Field of
Search: |
;556/419 ;549/214
;548/406 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Shaver; Paul F.
Attorney, Agent or Firm: Tolly; Lori D. Szala; Edwin M.
Claims
We claim:
1. A compound having the formula: ##STR17## wherein R is
independently selected from the group consisting of hydrogen, alkyl
of 1 to 3 carbon atoms and phenyl; R' is ##STR18## and n=1 to
6.
2. The compound of claim 1, wherein R is methyl, and n is 2 or
3.
3. The compound of claim 1, wherein the compound is
1,3-bis(4-aminophenoxy)-1,1,3,3-tetramethyldisiloxane bis-maleamic
acid; 1,3-bis(4-aminophenoxy)-1,1,3,3-tetramethyldisiloxane
bis-maleimide; or
1,3-bis(4-aminophenoxy)-1,1,3,3-tetramethyldisiloxane
bis-isomaleimide.
4. The compound of claim 1, wherein the compound is
1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane bis-maleamic
acid; 1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane
bis-maleimide; or
1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane
bis-isomaleimide.
5. The compound of claim 1, wherein the compound is
1,5-bis(3-aminophenoxy)-1,1,3,3,5,5-hexamethyltrisiloxane
bis-maleamic acid;
1,5-bis(3-aminophenoxy)-1,1,3,3,5,5-hexamethyltrisiloxane
bis-maleimide; or
1,5-bis(3-aminophenoxy)-1,1,3,3,5,5-hexamethyltrisiloxane
bis-isomaleimide .
6. A process for the preparation of the bis-maleamic acid siloxane
of claim 1, wherein R' is ##STR19## which comprises reacting a
diaminodiphenoxysiloxane of the formula ##STR20## wherein R and n
are as defined in claim 1, with maleic anhydride in at least a 1:2
molar ratio in an inert organic solvent at a temperature of
0.degree.-60.degree. C. and recovering the bis-maleamic acid
siloxane.
7. The process of claim 6, wherein the inert organic solvent is
acetone.
8. A process for the preparation of a bis-maleimide siloxane having
the formula ##STR21## wherein R is independently selected from the
group consisting of hydrogen, alkyl of 1 to 3 carbon atoms and
phenyl; n=1 to 6; and R' is ##STR22## which comprises reacting a
diaminodiphenoxysiloxane of the formula ##STR23## wherein R and n
are already defined, with maleic anhydride in at least a 1:2 molar
ratio in an inert organic solvent at a temperature of
0.degree.-60.degree. C.; cyclizing the maleated siloxane employing
a dehydrating agent at a temperature of 0.degree.-20.degree. C., in
the presence of a nucleophilic catalyst which is present as a
by-product of the maleation or which has been additionally added;
and recovering the bis-maleimide siloxane.
9. The process of claim 8 wherein the dehydrating agent is
N,N'-dicyclohexylcarbodiimide.
10. The process of claim 8 wherein the maleation reaction is
conducted in acetone, the maleated siloxane is recovered from said
acetone and the cyclization reaction is conducted in
dichloromethane.
11. The process of claim 8 wherein the nucleophilic catalyst is
additionally added in an amount of 40 to 200 weight percent based
on the maleated siloxane.
12. A process for the preparation of a bis-isomaleimide siloxane
having the formula ##STR24## wherein R is independently selected
from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms
and phenyl; n=1 to 6; and R' is ##STR25## which comprises reacting
a diaminodiphenoxysiloxane of the formula ##STR26## wherein R and n
are already defined, with maleic anhydride in at least a 1:2 molar
ratio in an inert organic solvent at a temperature of
0.degree.-20.degree. C.; cyclizing the maleated siloxane employing
a dehydrating agent at a temperature of 0.degree.-20.degree. C.;
and recovering the bis-isomaleimide siloxane.
13. The process of claim 12, wherein the dehydrating agent is
N,N'-dicyclohexylcarbodiimide.
14. The process of claim 12, wherein the maleation reaction is
conducted in acetone, the maleated siloxane is recovered from said
acetone, and the cyclization reaction is conducted in
dichloromethane.
15. A process for the isomerization of the bis-isomaleimide
siloxane of claim 12 to the corresponding bis-maleimide which
comprises isomerizing the bis-isomaleimide in the presence of a
nucleophilic catalyst in an inert organic solvent at a temperature
of 0.degree.-30.degree. C. and recovering the bis-maleimide
siloxane.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel aminophenoxysiloxane derivatives.
More specifically, this invention relates to maleated
aminophenoxysiloxanes.
2. Prior Art
Curable adhesive and sealant compositions employing maleimide
derivatives are well known in the art. For example, U.S. Pat. No.
3,988,299 (issued Oct. 26, 1976 to B. M. Malofsky) describes the
use of small amounts of maleimide derivatives with unsaturated
diacrylates in both heat curable and anaerobic curable adhesive
compositions. U.S. Pat. No. 4,370,467 (issued Jan. 25, 1983 to M.
Gaku et al.) describes the use of maleimides with polyfunctional
aromatic cyanate esters in the preparation of curable resin
compositions.
The use of bis-maleimides in the synthesis of various polyimides as
well as many other polymers including unsaturated hydrocarbon types
and polymers containing amino groups is also known. Bis-maleamic
acids and bis-maleimides have been used to crosslink natural rubber
as well, see J. Am. Chem. Soc., 81, 1187-94 (1959).
N,N'-disubstituted bis-isomaleimides are also known to react with
various diamines by free-radical polymerization or condensation
polymerization to yield high molecular weight polymaleamides, see
J. Polymer Science, 13, 1691-1698 (1975).
Polysiloxanes have also been described as useful in curable
adhesive compositions. See U.S. Pat. No. 4,370,358 (issued Jan. 25,
1983 to S. E. Hayes et al.) which describes the use of a radiation
curable composition for forming a pressure sensitive silicone
adhesive including an epoxy-containing siloxane polymer.
Liquid crystalline elastomers have been made wherein the polymer
network includes a polysiloxane main chain. As described in
Makromol. Chem., Rapid Commun. 2, 317 (1981), by incorporating the
polysiloxane unit, a high degree of flexibility is imparted to the
polymer.
The products of the present invention are maleated
aminophenoxysiloxane derivatives which contain both siloxane and
maleimide or maleamic acid moieties. None of the above references
disclose or suggest the products of the present invention.
SUMMARY OF THE INVENTION
According to the present invention, novel maleated
aminophenoxysiloxanes and a process for the preparation thereof are
herein provided.
The substituted siloxane derivatives of the present invention are
represented by formula I ##STR1## wherein R is independently
selected from the group consisting of hydrogen, alkyl of 1 to 3
carbon atoms and phenyl; R' is ##STR2## and n=1 to 6. Where n=1 it
is understood that the compound is a "silane" rather than a
siloxane. However, for purposes of this invention, the siloxane
term will include such silane compounds when appropriate as will be
apparent to those skilled in the art.
The substituted siloxane derivatives of the present invention are
prepared by reacting a diaminodiphenoxysiloxane of formula II
##STR3## wherein R and n have the meanings given under formula I,
with maleic anhydride to produce the diaminodiphenoxysiloxane
bis-maleamic acid. The maleamic acid may be further cyclized to
yield either the corresponding maleimide or isomaleimide
derivative.
PREPARATION OF STARTING MATERIALS
The diaminodiphenoxysiloxane II intermediates used in the present
invention are not commercially available; however, the preparation
of such materials is known in the literature. See, for example, J.
Polymer Sci. 7, 1089-1110 (1969). In providing the
diaminodiphenoxysiloxane derivatives of formula II,
dialkyldiaminosiloxanes or silanes of formula III ##STR4## wherein
R has the meaning given under formula I; R" is methyl or ethyl; and
n=0 to 5 are reacted with aminophenol. The desired orientation of
the resultant maleamic acid functionality on the aromatic ring of
the siloxane derivative I will determine which aminophenol isomer
should be used. Generally, two moles of aminophenol will be reacted
with one mole of siloxane or silane of formula III; however, a
small excess of aminophenol (about 10 molar percent) may be
employed if desired. The reaction is conducted in an inert aromatic
solvent such as benzene or toluene under a positive pressure of an
inert gas such as argon or nitrogen. In the laboratory, the
siloxane or silane of formula III is slowly added over a period of
1-2 hours to the aminophenol in solvent. During addition, the
reaction temperature is maintained at about 70.degree.-80.degree.
C. After addition is complete, the mixture is heated to reflux
temperatures of 70.degree.-100.degree. C. for about 2 hours whereby
the aminosilanephenol condensation reaction proceeds to form the
more stable silicon-oxygen bond of the aminophenoxysiloxane
derivative while distilling off the dialkylamine by-product as it
is formed. The resultant mixture is cooled to temperatures of about
15.degree. C. at which time excess aminophenol may be filtered from
the solution. The aminophenoxysiloxane of formula II may then be
recovered by distillation of the solvent.
The cited literature reference describes the preparation of
1,3-bis(4-aminophenoxy) tetramethyldisiloxane. The resultant
siloxane is further described as being an amber oil. Unexpectedly,
by the method of preparation described above and in Example 2, a
tan solid (m.p. 56.degree.-57.degree. C.) was obtained.
Dialkyldiaminosiloxanes and silanes of formula III are also not
commercially available but can be made from the respective
halosiloxanes or halosilanes and dialkylamines by the teachings
described in the J. Polymer Science, Vol. 7, reference mentioned
above. The halosiloxanes or halosilanes employed are of the general
formula IV ##STR5## wherein R has the meaning given under formula
I; X is a halogen selected from the group consisting of chlorine,
bromine, iodine, and fluorine and n=0 to 5. Suitable dialkylamines
employed include such short chain amines as dimethylamine and
diethylamine. The use of diethylamine is preferred.
In the laboratory, the halosiloxane or halosilane is slowly added
over a period of 1-2 hours to an excess amount of dialkylamine in
an inert solvent such as ether under anhydrous conditions and a
positive pressure of an inert gas such as argon or nitrogen. During
addition the reaction temperature is maintained at about
0.degree.-10.degree. C. After the addition is complete, the mixture
is then stirred for about 12-16 hours at ambient temperatures.
After the aminolysis reaction is complete, the amine hydrochloride
byproduct is filtered off and the dialkyldiaminosiloxane or silane
of formula III can be recovered by removal of the excess
dialkylamine and solvent through distillation.
Halosilanes as well as many of the halosiloxanes of formula IV are
commercially available and may be obtained from Petrarch Systems,
Inc. Other suitable halosiloxanes commercially unavailable may be
prepared by the general teachings of silicon chemistry. For
example, tetrachlorosilane or trichlorosilane will react with
appropriate Grignard reagents to produce substituted
dichlorosilanes. These dichlorosilanes may then undergo partial
hydrolysis to yield the desired dichlorosiloxanes.
PREPARATION OF NOVEL MALEATED SILOXANES
According to the present invention, maleation of a siloxane of
formula II is achieved by reacting maleic anhydride with the
siloxane in a molar concentration of about 2 to 3 moles of maleic
anhydride for one mole of the siloxane. The addition reaction is
conducted in an inert organic solvent such as acetone, toluene or
tetrahydrofuran. The use of acetone is preferred. In the
laboratory, a solution of maleic anhydride and solvent is added
slowly to a solution of the siloxane and solvent while maintaining
the reaction temperature below 10.degree. C. The reaction mixture
is stirred for an additional two hours at reduced temperatures
after addition to insure completion of the maleation reaction. The
resultant bis-maleamic acid derivatives precipitate from solution
and may be recovered in good yields by filtration without the need
for further purification.
It is noted that siloxanes, in general, are moisture-sensitive and
will cleave in the presence of water. Therefore, care must be taken
to conduct all reactions involving a siloxane in anhydrous solvents
under a positive pressure of an inert gas such as argon or
nitrogen. The use of argon is preferred because of its relative
high degree of dryness.
The cyclization of maleamic acids to isomaleimides and maleimides
is known in the literature. See, for example, U.S. Pat Nos.
4,132,715 and 4,179,444 (issued Jan. 2, 1979 and Dec. 18, 1979
respectively to M. Roth) which describe processes for the
manufacture of isomaleimides and maleimides. Maleamic acids may be
cyclized in a number of ways to form the corresponding
isomaleimides. Various dehydrating agents such as acid anhydrides
and acid halides, carbodiimides, and ketene have been used to
cyclize maleamic acids at temperatures of about
10.degree.-60.degree. C.
In cyclizing the maleamic acid siloxanes of the present invention,
care must be taken when choosing the method of dehydration. Some
dehydrating agents were found to cause siloxane cleavage. For
example, significant siloxane cleavage occurred when a maleamic
acid siloxane of formula I was treated with acetic anhydride and
sodium acetate in refluxing acetone at a temperature of about
55.degree. C. The use of N,N'-dicyclohexylcarbodiimide (DCC) in a
molar concentration of about two moles of DCC for one mole of
maleamic acid siloxane is the preferred dehydrating agent for the
cyclization reaction.
Cyclization of the maleamic acids to the corresponding
isomaleimides is performed in the presence of an organic solvent
which is inert under the reaction conditions. Suitable solvents
include various halogenated hydrocarbons, dioxane, and
tetrahydrofuran. The preferred solvent of choice is
dichloromethane. On a laboratory scale, the cyclization is
conducted by adding DCC to a cooled mixture of the maleamic acid
siloxane and solvent and stirring at 0.degree.-10.degree. C. for
about two hours. The mixture is then stirred at a temperature of
10.degree.-30.degree. C. for about 12-16 hours. Dicyclohexylurea
which forms during the reaction can be filtered from the solution
and the resultant isomaleimide can then be recovered by
distillation of the dichloromethane solvent.
U.S. Pat. No. 4,132,715 (mentioned above) describes the
isomerization of isomaleimides to the corresponding maleimides.
When in the presence of nucleophilic catalysts such as phenol and
triethylamine, isomaleimides rearrange to form maleimides.
It was discovered that when the maleation of aminophenoxysiloxanes
of formula II was conducted at temperatures of
45.degree.-50.degree. C., only corresponding maleimide derivatives
were later produced by the cyclization procedure described above.
It is believed that at such temperatures during maleation, maleic
anhydride causes some siloxane cleavage of the aminophenoxysiloxane
which results in the production of an amount of maleamic acid of
aminophenol. The phenol would be recovered with the
diaminodiphenoxysilane bis-maleamic acid derivative during
filtration. This nucleophilic impurity would then be present during
cyclization, thereby influencing the reaction such that only the
maleimide derivative would be formed instead of the expected
isomaleimide derivative. It was found that the cyclization reaction
produces the isomaleimide derivative first and if a nucleophilic
catalyst is present, the isomaleimide derivative rearranges to form
the corresponding maleimide with time.
Accordingly, maleimide derivatives of the present invention may be
produced by at least two methods. One method involves maleating the
siloxanes of formula II at 45.degree.-50.degree. C. and then
subsequently cyclizing the respective maleamic acids at
temperatures below 10.degree. C. in the presence of nucleophilic
impurities which were formed during maleation. A second method of
producing the maleimides involves maleating the siloxanes of
formula II at temperatures below 10.degree. C. and subsequently
cyclizing the respective maleamic acids in the presence of a
controlled amount of a nucleophilic catalyst which must be added
while employing the same cyclizing reaction conditions. Many
suitable nucleophiles may be employed, for instance, phenol,
1-hydroxybenzotriazole, and the maleamic acid of aminophenol.
Concentrations of about 40 to 200 mole percent based on maleamic
acid are recommended for the complete production of the maleimide,
with the preferred amount used being 40-50 mole percent.
The maleated siloxanes of formula I are beige or yellow materials
which may be either liquids or solids at room temperature. They are
useful as crosslinking agents in adhesive applications when
employed in amounts ordinarily used to provide a crosslinkable
formulation. These derivatives may be used in other polymeric
systems as well.
The following examples will further illustrate the embodiments of
the present invention. In the examples, all percentages are given
by weight and all temperatures are in degrees Celsius unless
otherwise noted.
EXAMPLE 1
Preparation of Bis(diethylamino)-1,1,3,3-Tetramethyldisiloxane
##STR6##
Diethylamine, 184 g. (2.50 mole) of 400 ml. of anhydrous ether were
added to a one-liter multi-necked round bottom flask equipped with
reflux condenser, pressure equalizing addition funnel, thermometer
and stirrer, which was maintained under a positive pressure of
argon. The solution was chilled with an ice water bath to
5.degree.-10.degree. C. during the dropwise addition of 100 g.
(0.50 mole) of 1,3-dichloro-1,1,3,3,-tetramethyldisiloxane. After
addition was completed the mixture was stirred overnight at room
temperature (20.degree.-25.degree. C.). The mixture was then
filtered and the filtrate was concentrated by rotary evaporation.
The resulting residue was distilled at reduced pressure and yielded
81 g. (0.29 mole; 60% theoretical) of V (b.p. 75.degree.-80.degree.
C., 2 mm. Hg.).
EXAMPLE 2
Preparation of
1,3-Bis(4-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane ##STR7##
A mixture of 27.3 g. (0.25 mole) of p-aminophenol and 200 ml. of
toluene was added to a 500 ml. multi-necked round bottom flask
equipped with distillation condenser, pressure equalizing addition
funnel, thermometer and stirrer, and was maintained under a
positive pressure of argon. The mixture was heated to 70.degree. C.
during the dropwise addition of 32.4 g. (0.12 mole) of compound V.
After addition was completed, the mixture was heated for 2.5 hours
to a temperature where a very slow distillation began. The reaction
mixture was cooled to 15.degree. C. and filtered. The filtrate was
concentrated on a rotary evaporator to a volume of 75 ml then
chilled in a freezer. The diaminodiphenoxysiloxane VI precipitated
and was filtered yielding 35.7 g. (0.102 mole; 85% theoretical).
Recrystallization of VI from toluene gave a tan solid (m.p.
56.degree.-57.degree. C.).
Analysis for C.sub.16 H.sub.24 N.sub.2 O.sub.3 Si.sub.2
(MW=348.56): MW by neutralization equivalent=350.35. Calculated: C,
55.14%; H, 6.94%; N, 8.03%. Found: C, 56.04%; H, 7.05%; N,
7.49%.
EXAMPLE 3
Preparation of
1,3-Bis(4-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane Bis-maleamic
Acid ##STR8##
Compound VI, 16.2 g. (0.046 mole) and 100 ml. of acetone were added
to a 500 ml. multi-neck round bottom flask equipped with condenser,
pressure equalizing additional funnel, thermometer and stirrer,
which was maintained under a positive pressure of argon. A solution
of 11 g. (0.11 mole) of maleic anhydride in 50 ml of acetone was
added dropwise. Upon completion of the addition, the mixture was
heated to 45.degree.-50.degree. C. for 2 hours then cooled to
15.degree. C. in an ice bath. The precipitated bismaleamic acid VII
was filtered, yielding 12.6 g. (0.023 mole, 50% theoretical).
Recrystallization of a small portion of VII gave a yellow
crystalline solid (m.p. 177.degree.-180.degree. C.).
Analysis for C.sub.24 H.sub.28 N.sub.2 O.sub.9 Si.sub.2 (MW=544):
MW by neutralization equivalent=543.9. Calculated: C, 52.94%; H,
5.15%; N, 5.15%; Si, 10.29%. Found: C, 52.63%; H, 5.19%; N, 5.17%;
Si, 9.68%.
IR (KBr) 3290 and 3220 cm.sup.-1 (CONH), 3100 and 1705 cm.sup.-1
(COOH), 1635 and 1510 cm.sup.-1 (broad, CONH), 1260 cm.sup.-1
(Si(CH.sub.3).sub.2) 1065 cm.sup.-1 (Si--O--Si).
EXAMPLE 4
Preparation of
1,3-Bis(4-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane Bis-maleimide
##STR9##
A mixture of 10 g. (0.018 mole) of compound VII and 100 ml. of dry
dichloromethane was added to a 250 ml. multi-necked round bottom
flask equipped with condenser, thermometer and stirrer, and
maintained under a positive pressure of argon. The mixture was
cooled to 0.degree.-5.degree. C. with an ice water bath then 7.5 g.
(0.036 mole) of N,N'-dicyclohexylcarbodiimide (DCC) was added. The
mixture was stirred 2 hours at 5.degree.-10.degree. C. then
overnight at room temperature (20.degree.-25.degree. C.). The
N,N'-dicyclohexylurea by-product was filtered and washed with
dichloromethane. The filtrate and washings were concentrated on a
rotary evaporator to yield a yellow oil which was triturated with
low boiling petroleum ether to remove unreacted DCC. On further
concentration of residual petroleum ether, the product solidified
to yield 5.0 g (0.010 mole; 55% theoretical). Recrystallization of
VIII from toluene gave a yellow crystalline solid (m.p.
148.degree.-150.degree. C.).
Analysis for C.sub.24 H.sub.24 N.sub.2 O.sub.7 Si.sub.2 :
Calculated: C, 56.67%; H, 4.76%; N, 5.51%; Si, 11.04%. Found: C,
57.09%; H, 4.76%; N, 5.40%; Si, 11.57%.
IR(KBr) 1710 cm.sup.-1 (C.dbd.O), 1255 cm.sup.-1
(Si(CH.sub.3).sub.2), 1080 cm.sup.-1 (Si--O--Si).
'HNMR (CD.sub.2 Cl.sub.2), .delta. 0.08 (s, 12H, SiCH.sub.3), 7.00
(m, 12H, olefinic and aromatic).
.sup.13 CNMR (CD.sub.2 Cl.sub.2), .delta. 0.454, 120.704, 125.508,
128.195, 134.469, 154.275, 170.119 ppm.
EXAMPLE 5
Preparation of
1,3-Bis(3-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane Bis-maleamic
Acid ##STR10##
Using the procedure described in Example 2,
1,3-Bis(3-aminophenoxy)-1, 1,3,3-tetramethyldisiloxane (IX) was
prepared using m-aminophenol. In a flask equipped as in Example 3,
a solution of 16.2 g. (0.046 mole) of IX and 150 ml. acetone was
maintained at 5.degree.-10.degree. C. in an ice water bath while a
solution of 11 g. (0.11 mole) of maleic anhydride in 50 ml. of
acetone was added dropwise. After the addition was completed, the
reaction was stirred for an additional 2 hours at
5.degree.-10.degree. C. The precipitated maleamic acid derivative X
was filtered yielding 22 g. (0.040 mole, 87% theoretical) of
product. Recrystallization of a small portion of the acid from
methanol/tetrahydrofuran (95/5) gave a solid (m.p.
162.degree.-164.degree. C.).
Analysis for C.sub.24 H.sub.28 N.sub.2 O.sub.9 Si.sub.2 (MW=544):
MW by neutralization equivalent=543.7. Calculated: C, 52.9%; H,
5.15%; N, 5.15%; Si, 10.29%. Found: C, 52.95%; H, 5.43%; N, 5.06%;
Si, 9.72%.
IR (KBr) 3300 and 3230 cm.sup.-1 (CONH), 3100 and 1710 cm.sup.-1
(COOH), 1635, 1575, 1535 amd 1410 cm.sup.-1 (CONH), 1270 cm.sup.-1
(Si(CH.sub.3).sub.2), 1085 cm.sup.-1 (Si--O--Si).
.sup.13 CNMR (DMSO-d.sub.6), .delta. 0.648, 111.031, 113.041,
115.057, 129.534, 130.251, 131.742, 139.601, 153.948, 163.168,
166.612 ppm.
EXAMPLE 6
Preparation of
1,3-Bis(3-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane
Bis-isomaleimide ##STR11##
The above compound was prepared from Compound X employing the
reaction conditions of Example 4. A yellow oil was recovered in 83%
yield.
Analysis yielded the following:
IR (Neat) 1805 cm.sup.-1 (C.dbd.O), 1690 cm.sup.-1 (C.dbd.N), 1275
cm.sup.-1 (Si(CH.sub.3).sub.2), 1090 cm.sup.-1 (Si--O--Si).
'HNMR (CDCl.sub.3), .delta. 0.20 (s, 12H, Si--CH.sub.3), 7.10
(complex m, 12H, olefin and aromatic).
.sup.13 CNMR (CDCl.sub.3), .delta. 0.583, 116.548, 118.496,
118.885, 127.913, 129.534, 143.039, 144.468, 150.182, 154.597,
166.934 ppm.
EXAMPLE 7
Preparation of
1,3-Bis(4-aminophenoxy)-1,1,3,3-Tetramethyldisiloxane
Bis-Isomaleimide ##STR12##
1,3-Bis(4-aminophenoxy)-1,1,3,3-tetramethyldisiloxane bis-maleamic
acid (VII) was prepared from Compound VI employing the maleation
reaction conditions of Example 5. Compound XII was prepared by
reacting 10 g. (0.018 mole) of VII with 7.5 g. (0.036 mole) of DCC
as described in Example 4. A yellow solid (m.p.
130.degree.-132.degree. C.) was recovered in 100% yield.
Analysis for C.sub.24 H.sub.24 N.sub.2 O.sub.7 Si.sub.2 :
Calculated: C, 56.59%; H, 4.96%, Si, 11.04%. Found: C, 56.83%; H,
4.93%; Si, 10.44%.
IR (KBr) 1795 cm.sup.-1 (C.dbd.O), 1680 cm.sup.-1 (C.dbd.N), 1270
and 800 cm.sup.-1 (Si(CH.sub.3).sub.2), 1080 cm.sup.-1
(Si--O--Si).
'HHMR (CD.sub.2 Cl.sub.2), .delta. 0.15 (s, 12H, SiCH.sub.3), 7.00
(m, 12H, olefinic and aromatic).
.sup.13 CNMR (CD.sub.2 Cl.sub.2), .delta. 0.388, 120.641, 127.394,
128.043, 138.105, 143.756, 149.403, 154.338, 167.843 ppm.
EXAMPLE 8
Preparation of
1,5-Bis(diethylamino)-1,1,3,3,5,5-Hexamethyltrisiloxane
##STR13##
Analogously to the procedure described in Example 1, 159 g. (0.57
mole) of 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane were
reacted with 209.5 g. (2.80 mole) of diethylamine to yield 180 g.
(0.51 mole; 89% theoretical) of XIII (b.p. 100-102 C., 2.5 mm
Hg).
EXAMPLE 9
Preparation of
1,5-Bis(3-aminophenoxy)-1,1,3,3,5,5-Hexamethyltrisiloxane ##STR14##
The above compound was prepared by reacting 20 g. (0.057 mole) of
compound XIII with 12.5 g. (0.114 mole) of m-aminophenol in 300 ml.
of toluene employing the reaction conditions of Example 2 yielding
24 g. (0.057 mole, crude) of XIV, a near colorless oil.
EXAMPLE 10
Preparation of
1,5-Bis(3-aminophenoxy)-1,1,3,3,5,5-Hexamethyltrisiloxane
Bis-maleamic acid ##STR15##
This compound was prepared analogously to the procedure described
in Example 5 with 24 g. of XIV, 11.7 g. (0.12 mole) of maleic
anhydride, and 200 ml. of acetone, yielding 24 g. (0.039 mole; 68%
theoretical). Recrystallization from cyclohexane/acetone gave a
solid (m.p. of 146.degree.-148.degree. C.).
Analysis for C.sub.26 H.sub.34 N.sub.2 O.sub.10 Si.sub.3 (MW=619):
MW by neutralization equivalent=616. Calculated: C, 50.46%; H,
5.53%; N, 4.53%; Si, 13.62%. Found: C, 50.01%; H, 5.33%; N, 4.48%;
Si, 12.20%.
IR (KBr) 3290 and 3220 cm.sup.-1 (CONH), 3100 and 1705 cm.sup.-1
(COOH), 1635-1500 cm.sup.-1 (broad, CONH), 1260 and 795 cm.sup.-1
(Si(CH.sub.3).sub.2), 1045 cm.sup.-1 (Si--O--Si).
EXAMPLE 11
Preparation of
1,5-bis(3-aminophenoxy)-1,1,3,3,5,5-Hexamethyltrisiloxane
Bis-isomaleimide ##STR16##
A mixture of 20 g. (0.032 mole) of XV and 13.2 g. (0.064 mole) of
DCC were reacted in 150 ml. of dichloromethane employing the same
reaction conditions of Example 4 yielding 17.5 g. (0.03 mole; 94%
theoretical) of a yellow oil.
Analysis yielded the following: IR (Neat) 1800 cm.sup.-1 (C.dbd.O),
1685 cm.sup.-1 (C.dbd.N), 1260 and 800 cm.sup.-1
(Si(CH.sub.3).sub.2), 1070 cm.sup.-1 (Si--O--Si).
'HNMR (CDCl.sub.3), .delta. 0.03 (s, 6H, SiCH.sub.3), 0.11 (s, 12H,
SiCH.sub.3), 7.00 (m, 12H, olefinic and aromatic).
.sup.13 CNMR (CDCl.sub.3), .delta. 0.648, 0.778, 116.486, 118.303,
118.755, 127.846, 129.404, 142.978, 144.535, 150.120, 154.727,
166.872 ppm.
EXAMPLE 12
This example illustrates the isomerization of
1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane
bis-isomaleimide to the corresponding bis-maleimide in the presence
of a nucleophilic catalyst.
To a solution of XI (prepared as in Example 6) and dry
dichloromethane at room temperature, was added 40 mole percent of
N-(4-hydroxyphenyl)maleimide. The solution was stirred under argon
overnight then concentrated by rotary evaporation. IR analysis
showed the disappearance of the isomaleimide peaks at 1805
cm.sup.-1 and 1690 cm.sup.-1 and the appearance of a strong peak at
1720 cm.sup.-1 indicative of the normal maleimide.
EXAMPLE 13
This example describes the preparation of
1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane bis-maleimide
from the corresponding bismaleamic acid in the presence of a
nucleophilic catalyst.
Following the procedure of Example 4, DCC as well as 40 mole
percent of N-(4-hydroxyphenyl) maleamic acid is added to a cooled
solution of X (prepared as in Example 5) and dichloromethane. Upon
completion of the reaction, the resulting product should be the
bis-maleimide.
Summarizing, novel maleated aminophenoxysiloxanes and a process for
the preparation thereof are provided diaminodiphenoxysiloxanes are
maleated and may be further cyclized to yield maleimide and
isomaleimide derivatives.
The preferred embodiments of the present invention having been
described above, various modifications and improvements thereon
will now become readily apparent to those skilled in the art.
Accordingly, the spirit and scope of the present invention is
defined not by the foregoing disclosure, but only by the appended
claims.
* * * * *